Silicone polymers, copolymers and block copolymers and a method for their preparation

ABSTRACT

Novel silicone acrylate polymers and a method for their preparation is disclosed. These polymers are formed from silicone acrylates, silicone diacrylates, or mixtures with organic acrylates. The copolymer formed from the reaction mixture of silicone acrylates and organic acrylates is useful in enhancing glass reinforced polyesters.

This invention relates to novel silicone acrylate polymers, copolymersand block copolymers. This invention also relates to a novel method usedto produce the silicone polymers, copolymers and block copolymers. Thisinvention also relates to improvement of glass reinforced polyesters bythe addition of silicon acrylate copolymers to the glass.

BACKGROUND OF THE INVENTION

Polymerization of organic acrylate monomers or mixtures thereof is wellknown in the art. One such method as described in U.S. Pat. Nos.4,417,034 to Webster and 4,414,372 to Farnham et al. teaches a method inwhich the acrylate is polymerized in the presence of a catalyst and aninitiator. This method is commonly referred to as Group TransferPolymerization. The acrylates introduced into the reaction can be of onespecies producing homopolymers or several different species producingcopolymers. Because of the ability to create "living" polymers it ispossible to produce both random and structured copolymers by controllingthe order of addition of materials.

A "living" polymer, as defined by Webster and by Farnham, et al., is onewhich contains active terminal group(s) and is capable of polymerizingfurther in the presence of the catalyst and an acrylate. A terminated,or non-living, polymer is not capable of further polymerization by thegroup transfer polymerization method.

A common initiator for this process is a silyl ketene acetal. Althoughthis is a siloxy-functional compound it is never incorporated into thepolymer unless the polymer is maintained in the living form. At thatpoint it is incorporated only at the polymer ends and is not along thepolymer backbone. The siloxy functionality is removed from the polymerends when the living form is terminated.

Numerous pieces of literature report on the studies that have been doneon the types of acrylates, catalysts, and initiators that are applicablein the above described method for acrylate polymerization. Of theacrylates studied the number that contain silicones or siloxanes appearsto be limited. It also appears that the use of organic diacrylates andsilicone diacrylates which result in block copolymers has also beenlimited.

Both Farnham et al. and Webster teach the use of siloxy containingacrylates for use in the polymerization process. These compounds likethe initiator are present along the polymer chain while in the livingform. However upon termination of the reaction the siloxy group isremoved from the polymer backbone resulting in a polymer that isessentially organic.

U.S. Pat. No. 4,588,795 to Dicker et al. teaches novel catalysts whichare useful in the method as taught by Farnham et al. and Webster. Thesecatalysts, in particular, are oxyanions and salts comprising suitablecations.

Other methods have been developed for acrylate polymerization. Most ofthese result in a polydispersed polymer, i.e. high molecular weightdistribution, and require the use of a peroxide type catalyst for freeradical addition.

Novelty arises in this invention due to the use of silicone acrylatesthat are incorporated into the polymer backbone, in both living andnon-living form, and the ability to provide monodispersed polymers orthose with a narrow molecular weight distribution.

It is an object of this invention to show novel silicone acrylatepolymers, copolymers and block copolymers produced from siliconeacrylates, silicone diacrylates, organic acrylates and mixtures thereof.

It is also an object of this invention to show a novel method forproducing silicone acrylate block copolymers.

It is also an object of this invention to show improved glass reinforcedpolyesters by the addition of silicon acrylate polymers or copolymers tothe glass.

THE INVENTION

In this invention monomers of silicone mono-acrylates or diacrylates(herein referred to only by silicone acrylate) and silicone acrylate ordiacrylate/organic acrylate mixtures (herein referred to by acrylatemixture) are reacted to form novel polymers. The reaction requires theuse of a catalyst and an initiator as well as the monomers of thedesired silicone acrylate or acrylate mixture to create the polymers.These polymers may be produced as living polymers or can be terminated,producing a non-living polymer, by treating them when the desired degreeof reaction has been achieved.

Various types of polymers can be produced by the method of thisinvention. These include living and non-living homopolymers, copolymersor block copolymers. Any of the aforesaid polymers can be structured,those that contain specific units along the polymer chain, or random,those that contain no set structure along the polymer chain.

Silicone acrylates useful in this invention are of the general formula##STR1## wherein R¹ is selected from a straight or branched chainalkylene group having 1 to 6 carbons and an arylene group having 6 to 10carbons; R² is selected from the methyl group and the hydrogen atom; andeach R³ is independently selected from an alkyl or alkoxy group having 1to 4 carbons and an aryl group having 6 to 10 carbons.

Silicone diacrylates useful in this invention are of the generalformula: ##STR2## wherein R¹ and R² are described as previously; each R⁴is independently selected from an alkyl group having 1 to 4 carbons oran aryl group having 6 to 10 carbons; and x has the value of 1 to 25.

The above mentioned silicone acrylates (I and II) may be usedindependently, in mixtures thereof or in mixtures with organic acrylatesof the formula

    CH.sub.2 ═C(Y)X                                        (III)

or ##STR3## wherein X is selected from --CN, --CH═CHC(O)X' or --C(O)X';

Y is selected from --H, --CH₃, --CN or --CO₂ R provided that Y is --H or--CH₃ when X is --CH═CHC(O)X';

X' is selected from --R, --OR, or --NR⁵ R⁶ ;

R is selected from an alkyl, alkenyl, or alkadienyl group having 1 to 20carbons and an aryl, alkaryl or aralkyl group having 6 to 20 carbons;any of said groups optionally containing one or more ether oxygen atomswithin the aliphatic segments thereof; and optionally containing one ormore functional substituents that are unreactive in said reaction; and

each of R⁵ and R⁶ is independently selected from an alkyl group having 1to 4 carbons.

Organic acrylate monomers useful in this invention and commerciallyavailable may be further exemplified by methyl acrylate, methylmethacrylate, butyl methacrylate, sorbyl acrylate and methacrylate,lauryl methacrylate, ethyl acrylate, butyl acrylate, acrylonitrile,methacrylonitrile, 2-ethylhexyl methacrylate, 2-(dimethylamino)ethylmethacrylate, 2-(diethylamino)ethyl acrylate, 3,3-dimethoxypropylacrylate, 3-methacryloxypropyl acrylate, 2-acetoxyethyl methacrylate,p-tolyl methacrylate, N,N-dimethyl acrylamide, 2-methacryloxyethylacrylate, glycidyl methacrylate, 3-methoxypropyl acrylate,phenylacrylate, allyl acrylate and methacrylate. The preferred organicmonomer in this invention is methyl methacrylate.

Initiators useful in this invention are of the general formula (R⁷)₃ SiZwherein each R⁷ is independently selected from an alkyl group having 1to 10 carbons and an aryl or alkaryl group having 6 to 10 carbons; Z isselected from the following activating groups, ##STR4## and mixturesthereof wherein: X' is --OSi(R⁷)₃, --R, --OR, AND --NR⁵ R⁶ ;

each of R' and R" is independently selected from the hydrogen atom, analkyl or alkenyl group having 1 to 10 carbons, an aryl, alkaryl, andaralkyl group containing 6 to 10 carbons; any of said groups optionallycontaining one or more ether oxygen atoms within aliphatic segmentsthereof and optionally containing one or more functional substituentsthat are unreactive in said reaction;

R, R⁵, R⁶ and R⁷ are as previously described

Z' is selected from O and N;

m has the value of 2 to 4

n has the value of 3 to 5.

Organostanne and organogermane initiators may also be useful in thisinvention when they are of similar structure as the siloxy functionalinitiators described previously.

These initiators may be further exemplified by{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane;2-(trimethylsilyl)iso-butyronitrile; ethyl 2-(trimethylsilyl)acetate;trimethylsilyl nitrile; {(4,5-dihydro-2-furanyl)oxy}trimethylsilane;{(2-methyl-1-propenyldiene)bis(oxy)bis [trimethylsilane};{2-methyl-1-{2-methoxymethoxy)ethoxy}-1-propenyl)oxy}trimethylsilane;methyl {(2-methyl-1-(trimethylsilyloxy)-1-propenyl)oxy}acetate;{(1-(1-methoxymethoxy)-2-methyl-1-propenyl)oxy}trimethylsilane;{(2-ethyl-1-propoxy-1-butenyl)oxy}ethyldimethylsilane;2-(trimethylsilyl)propanenitrile;{(1-((1-dec-2-enyl)oxy)-2-methyl-1-propenyl)oxy}trimethylsilane; methyl2-(triethylsilyl(acetate;{(1-methoxy-2-methyl-1-propenyl)oxy}-phenyldimethylsilane;{(2-methyl-1-[2-trimethylsiloxy)ethoxy}-1-(propenyl)oxy]trimethylsilane;and others.

The initiators useful in this compound are either commerciallyavailable, known compounds, or prepared from known starting materials.Initiators should be used in levels of 0.1 to 10 percent by weight basedon the quantity of silicone acrylate or acrylate mixture present. Thepreferred initiator of this invention is{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane.

The activating group of the initiator, -Z, is incorporated onto apolymer end. Incorporation of the activating group at the polymer endcan provide sites suitable for further reactions such as cross linking,chain extension, and chain branching and for polymer modification by UVradiation, water sorption and others. The remaining portion of theinitiator, (R⁷)₃ Si--, is incorporated onto the opposite polymer endwhen the polymer is in the living form. Upon termination, the group(R⁷)₃ Si-- is removed from the polymer end through reaction with ahydroxylic material.

Catalysts useful in this invention are those which are anionsparticularly those that contain a source of fluoride, cyanide, azideions or are oxy-anions. The oxy-anions include carboxylate, phenolate,sulfinate, phosphinate, sulfonamidate and perfluoroalkoxide anions.These catalysts are either known compounds or can be prepared from knownstarting materials. Examples of those useful in this inventiontris(dimethyamino)sulfonium bifluoride, 3-chlorobenzoate,tetrabutylammonium fluoride, tris(dimethylamino)sulfoniumdifluorotrimethylsilicate, tris(dimethylamino)sulfonium cyanide,tetraphenylarsonium cyanide, tris(dimethylamino)sulfonium azide,tetraethylammonium azide, tetramethylammonium fluoride,tetraethylammonium cyanide, 4-cyanobenzoate, phenolate,4-trifluoromethyl benzoate, 3-nitrobenzoate and others. The preferredcatalysts are 3-chlorobenzoate and tetrabutylammonium fluoride.

Catalysts should be used at levels of 0.01 to 5 percent by weight basedon the quantity of silicone acrylate or acrylate mixture present. Thecatalyst may be used in its pure form or it may be dissolved in asuitable solvent. If a solvent is chosen it must be one that thecatalyst is sufficiently soluble in.

Although catalysts containing fluoride are useful in this invention,degradation of the silicone acrylate may occur in their presence. Thisdegradation may possibly only be in amounts equal to the concentrationof the catalyst employeed.

The process for preparing the polymers is preferably carried out bycombining the silicone acrylate or acrylate mixture, the catalyst andthe initiator at ambient temperature but may also be done attemperatures ranging from about -100° C. to 150° C. The process mayrequire a period of initiation before any visible reaction takes place.By visible it is meant any noticeable change in the process conditions,such as composition, phase, temperature and pressure, that is broughtabout through the resulting reaction.

The introduction of the materials into the reaction can be varied. Onesuch method is to add the catalyst to a solution containing the siliconeacrylate or acrylate mixture and the initiator. Another method is to addthe initiator to a solution containing the silicone acrylate or acrylatemixture and the catalyst. A third such method is to add the siliconeacrylate or acrylate mixture to a solution containing the catalyst andthe initiator. The preferred method is to add the catalyst to a solutioncontaining the silicone acrylate or acrylate mixture and initiator.

The reaction may also be carried out in the presence of a solvent.Solvents suitable in this invention are aprotic liquids in which thecatalyst, initiator, and acrylates are sufficiently soluble for thereaction to occur. These solvents should be relatively free of water orother hydroxylic contaminants when creating living or structuredpolymers. These solvents may be further exemplified by ethyl acetate,proprionitrile, toluene, xylene, bromobenzene, dimethoxyethane,diethoxyethane, diethylether, N,N-dimethyl-formamide,N,N-dimethylacetamide, N-methylpyrrolidone, anisole, acetonitrile,tetrahydrofuran and others.

If an acrylate mixture is being used the addition of the varyingacrylates can be carried out in two ways. The first is to combine themtogether and introduce them both simultaneously into the reactionmixture. The other way is to introduce them separately, allowing eachone to react completely before introducing the next. When adding eachacrylate independently it may be necessary to add additional amounts ofcatalyst for the reaction to proceed.

If using an acrylate mixture, the ratio of silicone acrylate to organicacrylate used to form the polymer can be varied. Mixtures, from thosethat are essentially all silicone acrylates and contain small amounts oforganic acrylates to those that are essentially all organic and containsmall quantities of silicone are applicable. The preferred ratio whenproducing polymers from acrylate mixtures is from 0.1:1 moles ofsilicone acrylate to organic acrylate to 20:1 mole of silicone acrylateto organic acrylate. Mixtures of various silicon acrylates are alsouseful and may contain levels of each silicone acrylate necessary toachieve any desired properties.

The reaction, producing living polymers, may be terminated, therebyproducing non-living polymers, by the addition of a hydroxylic substanceinto the reaction mixture. This hydroxylic substance may be introducedinto the polymer by the addition of materials such as methanol or water,exposure of the living polymer to moisture in the air or by contactingit with an aprotic solvent that is not free of moisture. If a hydroxylicmaterial is initially present in the reaction mixture it is possible todirectly produce a non-living polymer.

Polymers produced by the method of this invention using siliconediacrylates or silicone diacrylate/organic acrylate mixtures haveapplications in release coatings, contact lenses, electronics,adhesives, etching release, medical membranes, sealants, and othercoatings.

Polymers produced by the method of this invention using siliconemono-acrylates or silicone mono-acrylate/organic acrylate mixtures holdparticular usefulness as adhesion promoters in glass reinforcedpolyesters.

The glass reinforced polyesters are produced by diluting in alcohol thepolymer produced by the method of this invention in which a siliconeacrylate and organic acrylate mixture is reacted; coating glass fiberswith the polymer; allowing the alcohol to evaporate; applying apolyester to treated glass fibers and; curing the polyester.

These glass reinforced polyesters are produced by diluting the polymerproduced from a silicone acrylate and organic acrylate mixture in aalcohol. It is preferred that the polymer be in the non-living form. Thepreferred alcohol is isopropyl alcohol, however, alcohols such asmethanol, ethanol, butanol and others are applicable. A solution inwhich the polymer is emulsified in water may be useful as a method ofproviding a dilute solution of polymer for application to the glass.

The polymer is dissolved in the alcohol at concentrations from 0.01 to1.0 percent by weight and if desired can be allowed to stand at roomtemperature for a period of time or it may be used immediately. It ispreferred to maintain a solution consisting of 0.1 to 0.3 weight percentof the polymer in the alcohol.

The polymer/alcohol solution is applied to glass fibers until the fibersare completely wetted. Application may be achieved by methods such asdipping, spraying, wiping, pouring and others with care taken not todamage the fibers during the application process. The glass fiber mayfirst be cut to the desired strand length, left as a continuous unit,woven into a cloth or others before treating them with the siliconeacrylate polymer solution.

After treatment the fibers are dried to remove the alcohol. Thepreferred method for drying is to allow the fibers to stand (dripping)at room temperature for a period of time such that most of the alcoholis removed and then removing any remaining amounts of alcohol using asource of heat such as an oven or others.

The treated fibers are coated or mixed with the appropriatepolyester/catalyst solution and cured. Polyester systems that can becured at room temperatures or by the introduction of heat (heat cured)are useful. Polyesters and catalysts that are known and commerciallyavailable are applicable in this invention. Such systems may alsocontain accelerators or promoters. Examples of such Polyesters are ATLAC400 produced by ICI Americas (curable at room temperature) and KOPPERS6000-25 (curable with heat). Catalysts employed in this invention arealso those that are known and/or commercially available. These catalystsmay be further exemplified by benzoyl peroxide and methylethylketoneperoxide and others.

So that those skilled in the art can understand and appreciate theinvention taught herein, the following examples are presented, it beingunderstood that these examples should not be used to limit the scope ofthis invention over the limitation found in the claims attached hereto.

PREP-EXAMPLE I

Preparation of 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane,##STR5##

A stirred solution of 126 g (1.0 mole) of allyl methacrylate, 0.18 g(0.817 mmole) of 2,6-di-tert-butyl-4-methylphenol and 1.00 g of complexof chloroplatinic acid and 1,3-divinyltetramethyldisiloxane, preparedaccording the U.S. Pat. No. 3,419,593, under a 2% 02/98% N2 surfacesweep was heated to 75° C. To this was added 94.0 g (1.0 mole) ofdimethylchlorosilane at a rate to keep the temperature of the exothermicreaction at an average of 83° C. The resulting reaction mixture wasstripped removing volatiles at 65° C. and 0.1 mm Hg. Gas Chromatograph(GC) analysis confirmed the presence of 78 percent by weight of3-(chlorodimethyl-silyl)propyl methacrylate in the stripped reactionmixture.

786.2 g (43.7 mol) of water was added to a solution of 48 g (0.2 mole)of the 3-(chlorodimethylsilyl)propyl methacrylate and 72.0 g (1.0 mole)of tetrahydrofuran. This solution was allowed to sit under a hood untilall the volatiles had evaporated. The water layer was separated andremoved. The organic layer was washed with 500 ml of water, dissolved inethyl ether and dried over molecular sieves and magnesium sulfate. Theethyl ether was then allowed to evaporate under a hood. Eighty onepercent pure 1,3-bis(3-methacryoxypropyl)tetramethyldisiloxane wasobtained. Nuclear Magnetic Resonance Spectroscopy (NMR), InfraedSpectroscopy (IR), and Gas Chromatographic Mass Spectroscopy (GCMS) wereused to confirm the identification of the product.

PREP-EXAMPLE II

Preparation of ##STR6##

To a stirred solution of 200 g (0.1 mole) of ##STR7## 21.2 g (0.2) moleof triethylamine, 0.06 g (0.272 mmole) of2,6-di-tert-butyl-4-methylphenol, and 400 ml of n-pentane in a 1000 mlround bottom flask was added 21.9 g (0.21 mole) of methacryloylchloride. A thick white salt was formed. The salt mixture was filteredthrough a buchner funnel with Whatman #5 filter paper and the solventwas removed in vacuo. IR data confirmed that the desired dimethacrylate,2, had been formed by the presence of a carbonyl peak (--C(O)--O) andthe absence of an alcohol (--OH) peak.

PREP-EXAMPLE III

Preparation of 3-Chlorobenzoate Catalyst

A solution of 5.012 g (32 mmole) of 3-chlorobenzoic acid and 120 ml (49mmole) of tetrabutylammonium hydroxide was extracted three times with120 ml aliquots of methylene chloride. The resultant solution was thendried over sodium sulfate and filtered. Volatiles were removed in vacuoleaving a viscous oil which was dissolved and re-stripped three timeswith 100 ml aliquots of toluene. Upon the completion of the finalstripping, white crystals began to form. The oil/crystals were dissolvedin acetonitrile and gravity filtered. The acetonitrile was removed invacuo and 14.63 grams of catalyst recovered. Enough acetonitrile wasadded to make a 0.5M solution of 3-chlorobenzoate catalyst.

EXAMPLE 1

To a solution of 0.5 ml of methyl methacrylate, 0.5 ml siliconedimethacrylate, formula 2, and 0.1 g of{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane in a 2 oz. vial wasadded 0.1 gram of 0.5M 3-chlorobenzoate catalyst prepared previously.After 1 minute, the vial containing the reactants became warm to thetouch and a visible polymer formed.

EXAMPLE 2

To a mixture of 1.54 g (15 mmole) of methyl methacrylate, 0.20 g (0.98mmole) of silicone dimethacrylate, formula 2, and 0.09 g (0.52 mmole) of{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane in a 2 oz. vial wasadded 0.10 g of 0.5M 3-chlorobenzoate catalyst. An exothermic reactiontook place and a brittle polymer was quickly formed. This polymer wasless brittle than a pure methyl methacrylate (MMA) polymer formed by thesame reaction.

EXAMPLE 3

A solution of 1.5 g (15 mmole) of MMA, 0.31 g (0.152 mmole) of siliconedimethacrylate, formula 2, and 0.08 g (0.46 mmole) of{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane in 5.00 g oftetrahydrofuran was transferred by pipet to a 2 oz. vial. To thissolution was added 0.13 g of 0.5M 3-chlorobenzoate catalyst. A slightexothermic reaction occurred. A few drops of methanol were added toquench the presumed living polymer, the solution was poured into analuminum weighing dish, and the THF was allowed to evaporate. Severalhours later a clear and flexible polymer film remained in the aluminumdish.

EXAMPLE 4

To a stirred solution of 0.04 g (0.23 mmole) of{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane, 1.00 g (10 mmole)of methyl methacrylate, and 0.25 g (0.12 mmole) silicone dimethacrylate,formula 2, was added a solution of 4.0 g tetrahydrofuran and 0.03 g of0.5M 3-chlorobenzoate catalyst. An exothermic reaction resulted in apolymer. Gel Permeation Chromotography (GPC) data showed an averagemolecular weight of 1300 relative to polystyrene.

EXAMPLE 5

To 5 g of 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane, formula 1,was added 0.1 g of 3-chlorobenzoate catalyst followed by 0.1 g of{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane. An exothermicreaction occurred and within seconds a soft, flexible, and hazy to clearpolymer had formed.

EXAMPLE 6

Three different ratios of methylmethacrylate to silicone dimethacrylate,formula 1, were used to prepare the polymers. In each experiment a totalof 2 g of acrylate mixture, 5 g of tetrahydrofuran, 0.1 g of{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane and 0.1 g of 0.5M3-chlorobenzoate catalyst were used. Runs were conducted at ratios(molar) of 1:1 methyl methacrylate to silicone dimethacrylate, formula1, 5:1 and 10:1.

The general procedure use to prepare the polymers was to add the{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane to a 2 oz. vialcontaining the combined methacrylates and 3-chlorobenzoate catalyst intetrahydrofuran (THF). Upon completion of the reaction the livingpolymer was quenched with methanol. The polymer was then placed in analuminum dish and dried in vacuo in an oven at 50° C.

Each polymer resulted in different properties which are reported inTable I.

                  TABLE I                                                         ______________________________________                                        2 gram acrylates, oven dried                                                         Methacrylate Ratio                                                            1:1        5:1        10:1                                             ______________________________________                                        RESULTS  Exothermic   Exothermic Exothermic                                            Visible Gel  Clear      Clear                                                 THF trapped  THF trapped                                                                              MW = 6664                                             Clear polymer                                                                 After drying,                                                                 swelled in THF                                                       ______________________________________                                    

EXAMPLE 7

The same experiment was conducted as in Example 6 except only 1 gramtotal of the acrylates were used. Results are reported in Table II.

                  TABLE II                                                        ______________________________________                                        1 gram acrylates, oven dried                                                         Methacrylate Ratio                                                            1:1        5:1         10:1                                            ______________________________________                                        RESULTS  Exothermic   Exothermic  Exothermic                                           Visible Gel  Clear       Clear                                                THF trapped  MW = 5839   MW = 4482                                            Clear polymer                                                                 After drying,                                                                 swelled in THF                                                       ______________________________________                                    

EXAMPLE 8

The same experiment was conducted as in Example 7 except the polymerswere air dried in a hood at atmospheric pressure. Results are given inTable III.

                  TABLE III                                                       ______________________________________                                        1 gram acrylates, air dried                                                          Methacrylate Ratio                                                            1:1      5:1          10:1                                             ______________________________________                                        RESULTS  Exothermic Exothermic   Exothermic                                            Clear Film Clear Film   Clear Film                                            Tacky      Slightly Tacky                                                                             Smooth, hard                                                     Elastic      surface                                      ______________________________________                                    

EXAMPLE 9

A solution containing 10 grams (57.4 mmole) of{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane, 16 grams (64.5mmole) of gamma-methacryloxypropyltrimethoxysilane and 8 grams (63.3mmole) of allyl methacrylate was added dropwise over a period of 10minutes to a stirred solution containing 100 g tetrahydrofuran and 1.0ml tetrabutylammonium fluoride. An exotherm up to 55° C. was observedduring the addition. When the reaction mixture had cooled to 30° C. anexcess of methanol was added. Volatiles were removed in vacuo leaving aviscous (400 centistoke) fluid. GPC analysis showed a polymer with amolecular weight of 2500 and a polydispersity of 1.17.

EXAMPLE 10

A solution containing 10 grams (57.4 mmole) of{(1-methoxy-2-methyl-1-propenyl)oxy}trimethylsilane, 16 grams (64.5mmole) of gamma-methacryloxypropyltrimethoxysilane and 8 grams (63.3mmole) of allyl methacrylate was added dropwise over a period of 10minutes to a stirred solution containing 100 grams of tetrahydrofuranand 1.0 ml of tetrabutylammonium fluoride. During the addition thetemperature increased from 17° to 48° C. The reaction mixture wasstirred for 10 minutes. 2.1 grams (14.8 mmole) of glycidyl methacrylatewas added to the reaction mixture and stirred for 10 minutes. Anadditional 1 ml of tetrabutylammonium fluoride was added and stirred foran additional 10 minutes. Excess methanol was added and the volatileswere removed in vacuo leaving a polymer as the product.

EXAMPLE 11

300 grams of isopropyl alcohol was mixed with 0.6 grams of the polymerfrom example 9. Fiberglass cloth, style no. 7781, purchased fromBurlington Glass Fabrics Co. was cut into a 26"×38" section and foldedinto a 6"×12" square. The polymer/alcohol solution was poured into aceramic dish and the cloth was immersed into the solution until it wascompletely wetted. After soaking for about 1 minute, the cloth wasremoved and hung at room temperature for 30 minutes. It was then hung inan oven at 230° F. for 7 minutes.

The cloth prepared above was cut into (12) 8"×8" squares. 247.5 g ofKOPPERS 6000-25 (an isophthalic polyester containing approximately 35%styrene) and 2.5 g of benzoyl peroxide were mixed and allowed to standfor one hour. A laminate was formed by alternating layers of the (12)8"×8" sections of glass cloth and the polyester/catalyst solution. Afterallowing the laminate to stand for approximately 20 minutes at roomtemperature, a hard rubber roller was used to remove the air bubbles andcreate a relatively uniform thickness. The laminate was then pressed at250° C. in a 12"×12" WABASH Hydraulic Press Model #12-121 until 50 psiof pressure had been achieved and the laminate was 125 mils +/-3 milsthick. After 20 minutes in the press at 50 psi the 125 mil thicklaminate was removed and allowed to cool overnight. The cellophane wasremoved and the laminate was allowed an additional 4 hours at 250° F.for post cure.

Using 7/8"×4" sections of the laminate, flexural strength was tested perASTM 790D, Method I. Both dry flex and wet flex (24 hr. boil) weretested. A laminate (blank) was prepared as above except the glass wasnot treated with the polymer from example 9 for comparison purposes. Theblank had a dry flex of 47,690 psi and a wet flex of 22,113 psi whilethe polymer treated laminate had a dry flex of 46,049 psi and a wet flexof 35,727 psi.

EXAMPLE 12

Using the polymer of example 9, a 300 g solution of polymer and alcoholwas prepared and the cloth treated and dried as in example 11.

247 grams of ATLAC 400 ACT from ICI Americas (a terephthalic polyestercontaining approximately 45% styrene, accelerated with dimethyl anilineand promoted with cobalt Naphtenate) was mixed with 3 grams ofmethylethylketoneperoxide just prior to use.

A laminate was produced with the glass cloth and the polyester andallowed to stand at room temperature for about 15 minutes. It was placedin the press used in example 11 at room temperature (70° F.) until thepolyester had solidified (about 15 minutes). The laminate was removedfrom the press and allowed to postcure 16 hours at room temperature. Thecellophane was removed and the laminate was then post cured for anadditional 4 hours at 212° F.

The laminate and a blank were tested for wet and dry flex strength as inexample 11. The blank had a dry flex strength of 49,764 psi and a wetflex strength of 21,407 psi. The polymer treated laminate had a dry flexof 45,944 psi and a wet flex of 35,507 psi.

EXAMPLE 13

A laminate was prepared as in example 12 except the polymer from example10 was used. The laminate had a dry flex of 45,392 psi and a wet flex of33,142 psi.

What is claimed is:
 1. A process of making silicone acrylate polymericmaterials comprising(A) reactingi) an acrylate of the general formula##STR8## and mixtures thereof, in the presence of ii) an initiator ofthe formula (R⁷)₃ SiZ and, iii) a catalyst which is a source offluoride, cyanide, azide or oxy anions; (B) recovering the reactionproduct from (A); wherein: R¹ is selected from a straight or branchedchain alkylene group having 1 to 6 carbons and an arylene group having 6to 10 carbons; R² is selected from the methyl group and the hydrogenatom; each R³ is independently selected from an alkyl or alkoxy grouphaving 1 to 4 carbons and an aryl group having 6 to 10 carbons; each R⁷is independently selected from an alkyl group having 1 to 10 carbons andan aryl or alkaryl group having 6 to 10 carbons; and Z is selected fromthe group consisting essentially of ##STR9## and mixtures thereof whereX' is --OSi(R⁷)₃, --R, --OR, AND --NR⁵ R⁶ ;each of R' and R" isindependently selected from the hydrogen atom, an alkyl or alkenyl grouphaving 1 to 10 carbons, an aryl, alkaryl, and aralkyl group containing 6to 10 carbons; any of said groups optionally containing one or moreether oxygen atoms within aliphatic segments thereof and optionallycontaining one or more functional substitutents that are unreactive insaid reaction; Z' is selected from O and N; m has the value of 2 to 4; nhas the value of 3 to 5; each R is selected from an alkyl, alkenyl, oralkadienyl group having 1 to 20 carbons and an aryl, alkaryl or aralkylgroup having 6 to 20 carbons; any of said groups optionally containingone or more ether oxygen atoms within the aliphatic segments thereof;and optionally containing one or more functional substituents that areunreactive in said reaction; each R⁵ and R⁶ are independently selectedfrom an alkyl group having 1 to 4 carbons and; R⁷ is as defined above.2. A process as claimed in claim 1 wherein the acrylate isgamma-methacryloxypropyltrimethoxysilane.
 3. A process as claimed inclaim 1 wherein the initiator is of the formula ##STR10## where R⁷, R',R" and X' are as defined above.
 4. A process as claimed in claim 1wherein the catalyst is a source of oxy-anions.
 5. A process as claimedin claim 4 wherein the catalyst is 3-chlorobenzoate.
 6. A process ofmaking silicone acrylate polymeric materials comprising(A) reactingi) anacrylate of the general formula ##STR11## and mixtures thereof, in thepresence of ii) an initiator of the formula (R⁷)₃ SiZ and, iii) acatalyst which is a source of fluoride, cyanide, azide or oxy anions;(B) terminating said reaction by the introduction of a hydroxylicmaterial and; (C) recovering the reaction product from (B); wherein:R¹is selected from a straight or branched chain alkylene group having 1 to6 carbons and an arylene group having 6 to 10 carbons; R² is selectedfrom the methyl group and the hydrogen atom; each R³ is independentlyselected from an alkyl or alkoxy group having 1 to 4 carbons and an arylgroup having 6 to 10 carbons; each R⁷ is independently selected from analkyl group having 1 to 10 carbons and an aryl or alkaryl group having 6to 10 carbons; and Z is selected from the group consisting essentiallyof ##STR12## and mixtures thereof where X' is --OSi(R⁷)₃, --R, --OR, AND--NR⁵ R⁶ ; each of R' and R" is independently selected from the hydrogenatom, an alkyl or alkenyl group having 1 to 10 carbons, an aryl,alkaryl, and aralkyl group containing 6 to 10 carbons; any of saidgroups optionally containing one or more ether oxygen atoms withinaliphatic segments thereof and optionally containing one or morefunctional substituents that are unreactive in said reaction; Z' isselected from O and N; m has the value of 2 to 4; n has the value of 3to 5; each R is selected from an alkyl, alkenyl, or alkadienyl grouphaving 1 to 20 carbons and an aryl, alkaryl or aralkyl group having 6 to20 carbons; any of said groups optionally containing one or more etheroxygen atoms within the aliphatic segments thereof; and optionallycontaining one or more functional substituents that are unreactive insaid reaction; each R⁵ and R⁶ are independently selected from an alkylgroup having 1 to 4 carbons and; R⁷ is as defined above.
 7. A process ofmaking silicone acrylate polymeric materials comprising(A) reacting(i)an acrylate of the general formula ##STR13## and mixtures thereof, andii) an organic acrylate selected from the group consisting of ##STR14##and mixtures thereof, in the presence of iii) an initiator of theformula (R⁷)₃ SiZ, and iv) a catalyst which is a source of fluoride,cyanide, azide or oxy anions and; (B) recovering the reaction productfrom (A); wherein: R¹ is selected from a straight or branched chainalkylene group having 1 to 6 carbons and an arylene group having 6 to 10carbons; R² is selected from the methyl group and the hydrogen atom;each R³ is independently selected from an alkyl or alkoxy group having 1to 4 carbons and an aryl group having 6 to 10 carbons; R is selectedfrom an alkyl, alkenyl, or alkadienyl group having 1 to 20 carbons andan aryl, alkaryl or aralkyl group having 6 to 20 carbons; any of saidgroups optionally containing one or more ether oxygen atoms within thealiphatic segments thereof; and optionally containing one or morefunctional substituents that are unreactive in said reaction; X isselected from --CN, --CH═CHC(O)X', and --C(O)X'; Y is selected from --H,--CH₃, --CN or --CO₂ R provided that Y is --H or --CH₃ when X is--CH═CHC(O)X'; each R⁷ is independently selected from an alkyl grouphaving 1 to 10 carbons and an aryl or alkaryl group having 6 to 10carbons; Z is selected from the group consisting essentially of##STR15## and mixtures thereof where X' is --OSi(R⁷)₃, --R, --OR, AND--NR⁵ R⁶ ;each of R' and R" is independently selected from the hydrogenatom, an alkyl or alkenyl group having 1 to 10 carbons, an aryl,alkaryl, and aralkyl group containing 6 to 10 carbons; any of saidgroups optionally containing one or more ether oxygen atoms withinaliphatic segments thereof and optionally containing one or morefunctional substituents that are unreactive in said reaction; Z' isselected from O and N; m has the value of 2 to 4; n has the value of 3to 5; each R⁵ and R⁶ are independently selected from an alkyl grouphaving 1 to 4 carbons and; R and R⁷ are as defined above.
 8. A processas claimed in claim 7 wherein the acrylate isgamma-methacryloxypropyltrimethxoysilane.
 9. A process is claimed inclaim 7 wherein the initiator is of the formula ##STR16## where R⁷, R',R" and X' are defined above.
 10. A process as claimed in claim 7 whereinthe catalyst is a source of oxy-anions.
 11. A process as claimed inclaim 10 wherein the catalyst is 3-chlorobenzoate.
 12. A process asclaimed in claim 7 wherein the catalyst is tetra-N-butylammoniumfluoride.
 13. A process as claimed in claim 7 wherein the organicacrylate is allyl methacrylate.
 14. A process as claimed in claim 7wherein the organic acrylate is methyl methacrylate.
 15. A process asclaimed in claim 7 wherein the organic acrylate is glycidylmethacrylate.
 16. A process as claimed in claim 8 wherein the organicacrylate is a mixture consisting of allyl methacrylate and glycidylmethacrylate.
 17. A process of making silicone acrylate polymericmaterials comprising(A) reacting(i) an acrylate of the general formula##STR17## and mixtures thereof, and ii) an organic acrylate selectedfrom the group consisting of ##STR18## and mixtures thereof, in thepresence of iii) an initiator of the formula (R⁷)₃ SiZ, and iv) acatalyst which is a source of fluoride, cyanide, azide or oxy anions;(B) terminating said reaction by the introduction of a hydroxylicmaterial and; (C) recovering the reaction product from (B); wherein: R¹is selected from a straight or branched chain alkylene group having 1 to6 carbons and an arylene group having 6 to 10 carbons; R² is selectedfrom the methyl group and the hydrogen atom; each R³ is independentlyselected from an alkyl or alkoxy group having 1 to 4 carbons and an arylgroup having 6 to 10 carbons; R is selected from an alkyl, alkenyl, oralkadienyl group having 1 to 20 carbons and an aryl, alkaryl or aralkylgroup having 6 to 20 carbons; any of said groups optionally containingone or more ether oxygen atoms within the aliphatic segments thereof;and optionally containing one or more functional substituents that areunreactive in said reaction; X is selected from --CN, --CH═CHC(O)X', and--C(O)X'; Y is selected from --H, --CH₃, --CN or --CO₂ R provided that Yis --H or --CH₃ when X is --CH═CHC(O)X'; each R⁷ is independentlyselected from an alkyl group having 1 to 10 carbons and an aryl oralkaryl group having 6 to 10 carbons; Z is selected from the groupconsisting essentially of ##STR19## and mixtures thereof where X' is--OSi(R⁷)₃, --R, --OR, AND --NR⁵ R⁶ ;each of R' and R" is independentlyselected from the hydrogen atom, an alkyl or alkenyl group having 1 to10 carbons, an aryl, alkaryl, and aralkyl group containing 6 to 10carbons; any of said groups optionally containing one or more etheroxygen atoms within aliphatic segments thereof and optionally containingone or more functional substituents that are unreactive in saidreaction; Z' is selected from O and N; m has the value of 2 to 4; n hasthe value of 3 to 5; each R⁵ and R⁶ are independently selected from analkyl group having 1 to 4 carbons and; R and R⁷ are as defined above.18. A process of making silicone acrylate polymeric materialscomprising(A) reacting(i) a diacrylate of the general formula ##STR20##and mixtures thereof, in the presence of ii) an initiator of the formula(R⁷)₃ SiZ, and iii) a catalyst which is a source of fluoride, cyanide,azide or oxy anions and; (B) recovering the reaction product from (B);wherein: R¹ is selected from a straight or branched chain alkylene grouphaving 1 to 6 carbons and an arylene group having 6 to 10 carbons; R² isselected from the methyl group and the hydrogen atom; each R⁴ isindependently selected from an alkyl group having 1 to 4 carbons and anaryl group having 6 to 10 carbons; each R⁷ is independently selectedfrom an alkyl group having 1 to 10 carbons and an aryl or alkaryl grouphaving 6 to 10 carbons; and Z is selected from the group consistingessentially of ##STR21## and mixtures thereof where X' is --OSi(R⁷)₃,--R, --OR, AND --NR⁵ R⁶ ;each of R' and R" is independently selectedfrom the hydrogen atom, an alkyl or alkenyl group having 1 to 10carbons, an aryl, alkaryl, and aralkyl group containing 6 to 10 carbons;any of said groups optionally containing one or more ether oxygen atomswithin aliphatic segments thereof and optionally containing one or morefunctional substituents that are unreactive in said reaction; Z' isselected from O and N; m has the value of 2 to 4; n has the value of 3to 5; each R is selected from an alkyl, alkenyl, or alkadienyl grouphaving 1 to 20 carbons and an aryl, alkaryl or aralkyl group having 6 to20 carbons; any of said groups optionally containing one or more etheroxygen atoms within the aliphatic segments thereof; and optionallycontaining one or more functional substituents that are unreactive insaid reaction; each R⁵ and R⁶ are independently selected from an alkylgroup having 1 to 4 carbons and; R⁷ is as defined above.
 19. A processas claimed in claim 18 wherein the initiator is of the formula ##STR22##where R⁷, R', R" and X' are as defined above.
 20. A process as claimedin claim 18 wherein the catalyst is a source of oxy-anions.
 21. Aprocess as claimed in claim 20 wherein the catalyst is 3-chlorobenzoate.22. A process as claimed in claim 18 wherein R¹ is propylene, R² ismethyl and R⁴ is methyl.
 23. A process of making silicone acrylatepolymeric materials comprising(A) reacting(i) a diacrylate of thegeneral formula ##STR23## and mixtures thereof, in the presence of ii)an initiator of the formula (R⁷)₃ SiZ, and iii) a catalyst which is asource of fluoride, cyanide, azide or oxy anions; (B) terminating saidreaction by the introduction of a hydroxylic material and; (C)recovering the reaction product of (B). wherein: R¹ is selected from astraight or branched chain alkylene group having 1 to 6 carbons and anarylene group having 6 to 10 carbons; R² is selected from the methylgroup and the hydrogen atom; each R⁴ is independently selected from analkyl group having 1 to 4 carbons and an aryl group having 6 to 10carbons; each R⁷ is independently selected from an alkyl group having 1to 10 carbons and an aryl or alkaryl group having 6 to 10 carbons; and Zis selected from the group consisting essentially of ##STR24## andmixtures thereof where X' is --OSi(R⁷)₃, --R, --OR, AND --NR^(R) ⁶ ;eachof R' and R" is independently selected from the hydrogen atom, an alkylor alkenyl group having 1 to 10 carbons, an aryl, alkaryl, and aralkylgroup containing 6 to 10 carbons; any of said groups optionallycontaining one or more ether oxygen atoms within aliphatic segmentsthereof and optionally containing one or more functional substituentsthat are unreactive in said reaction; Z' is selected from O and N; m hasthe value of 2 to 4; n has the value of 3 to 5; each R is selected froman alkyl, alkenyl, or alkadienyl group having 1 to 20 carbons and anaryl, alkaryl or aralkyl group having 6 to 20 carbons; any of saidgroups optionally containing one or more ether oxygen atoms within thealiphatic segments thereof; and optionally containing one or morefunctional substituents that are unreactive in said reaction; each R⁵and R⁶ are independently selected from an alkyl group having 1 to 4carbons and; R⁷ is as defined above.
 24. A process of making siliconeacrylate polymeric materials comprising(A) reacting(i) a diacrylate ofthe general formula ##STR25## and mixtures thereof, and ii) an organicacrylate selected from the group consisting of ##STR26## and mixturesthereof, in the presence of iii) an initiator of the formula (R⁷)₃ SiZ,and iv) a catalyst which is a source of fluoride, cyanide, azide or oxyanions; and (B) recovering the reaction product of (A); wherein: R¹ isselected from a straight or branched chain alkylene group having 1 to 6carbons and an arylene group having 6 to 10 carbons; R² is selected fromthe methyl group and the hydrogen atom; each R⁴ is independentlyselected from an alkyl group having 1 to 4 carbons and an aryl grouphaving 6 to 10 carbons; R is selected from an alkyl, alkenyl, oralkadienyl group having 1 to 20 carbons and an aryl, alkaryl or aralkylgroup having 6 to 20 carbons; any of said groups optionally containingone or more ether oxygen atoms within the aliphatic segments thereof;and optionally containing one or more functional substituents that areunreactive in said reaction; X is selected from --CN, --CH═CHC(O)X', and--C(O)X'; Y is selected from --H, --CH₃, --CN or --CO₂ R provided that Yis --H or --CH₃ when X is --CH═CHC(O)X'; each R.sup. 7 is independentlyselected from an alkyl group having 1 to 10 carbons and an aryl oralkaryl group having 6 to 10 carbons; Z is selected from the groupconsisting essentially of ##STR27## and mixtures thereof where X' is--OSi(R⁷)₃, --R, --OR, AND --NR⁵ R⁶ ;each of R' and R" is independentlyselected from the hydrogen atom, an alkyl or alkenyl group having 1 to10 carbons, an aryl, alkaryl, and aralkyl group containing 6 to 10carbons; any of said groups optionally containing one or more etheroxygen atoms within aliphatic segments thereof and optionally containingone or more functional substituents that are unreactive in saidreaction; Z' is selected from O and N; m has the value of 2 to 4; n hasthe value of 3 to 5; each R⁵ and R⁶ are independently selected from analkyl group having 1 to 4 carbons and; R and R⁷ are as defined above.25. A process as claimed in claim 24 wherein the initiator is of theformula ##STR28## where R⁷, R', R" and X' are as defined above.
 26. Aprocess as claimed in claim 24 wherein the catalyst is a source ofoxy-anions.
 27. A process as claimed in claim 26 wherein the catalyst is3-chlorobenzoate.
 28. A process as claimed in claim 24 wherein R¹ ispropylene, R² is methyl and R⁴ is methyl.
 29. A process as claimed inclaim 24 wherein the organic acrylate is methyl methacrylate.
 30. Aprocess of making silicone acrylate polymeric materials comprising(A)reacting(i) a diacrylate of the general formula ##STR29## and mixturesthereof, and ii) an organic acrylate selected from the group consistingof ##STR30## and mixtures thereof, in the presence of iii) an initiatorof the formula (R⁷)₃ SiZ, and iv) a catalyst which is a source offluoride, cyanide, azide or oxy anions; (B) terminating said reaction bythe introduction of a hydroxylic material and; (C) recovering thereaction product of (B); wherein: R¹ is selected from a straight orbranched chain alkylene group having 1 to 6 carbons and an arylene grouphaving 6 to 10 carbons; R² is selected from the methyl group and thehydrogen atom; each R⁴ is independently selected from an alkyl grouphaving 1 to 4 carbons and an aryl group having 6 to 10 carbons; R isselected from an alkyl, alkenyl, or alkadienyl group having 1 to 20carbons and an aryl, alkaryl or aralkyl group having 6 to 20 carbons;any of said groups optionally containing one or more ether oxygen atomswithin the aliphatic segments thereof; and optionally containing one ormore functional substituents that are unreactive in said reaction; X isselected from --CN, --CH═CHC(O)X', and --C(O)X'; Y is selected from --H,--CH₃, --CN or --CO₂ R provided that Y is --H or --CH₃ when X is--CH═CHC(O)X'; each R⁷ is independently selected from an alkyl grouphaving 1 to 10 carbons and an aryl or alkaryl group having 6 to 10carbons; Z is selected from the group consisting essentially of##STR31## and mixtures thereof where X' is --OSi(R⁷)₃, --R, --OR, AND--NR⁵ R⁶ ;each of R' and R" is independently selected from the hydrogenatom, an alkyl or alkenyl group having 1 to 10 carbons, an aryl,alkaryl, and aralkyl group containing 6 to 10 carbons; any of saidgroups optionally containing one or more ether oxygen atoms withinaliphatic segments thereof and optionally containing one or morefunctional substituents that are unreactive in said reaction; Z' isselected from O and N; m has the value of 2 to 4; n has the value of 3to 5; each R⁵ and R⁶ are independently selected from an alkyl grouphaving 1 to 4 carbons and; R and R⁷ are as defined above.
 31. A siliconeacrylate polymer prepared by the method of claim
 1. 32. A siliconeacrylate polymer prepared by the method of claim
 6. 33. A siliconeacrylate polymer prepared by the method of claim
 7. 34. A siliconeacrylate polymer prepared by the method of claim
 17. 35. A siliconeacrylate polymer prepared by the method of claim
 18. 36. A siliconeacrylate polymer prepared by the method of claim
 23. 37. A siliconeacrylate polymer prepared by the method of claim
 24. 38. A siliconeacrylate polymer prepared by the method of claim 30.